We have already shown the synthetic procedure of 1,4-benzodiazepines from o-halo-anilines and amino acid derivatives by use of palladium catalyzed carbonylation. Using this method, the total syntheses of pyrrolo-1,4-benzodiazepine antibiotics, namely, tomaymycin, prothracarcin, and SEN-215 were achieved from o-haloaniline derivatives and hydroxy-l-proline as the optically active forms. The structures of prothracarcin and SEN-215 were determined synthetically as E-form, respectively. Moreover, a carbon framwork of neothramycin was constructed from o-iodoaniline and l-proline by four steps including palladium catalyzed carbonylation and anodic oxidation of carbon <alpha> to nitrogen. The total synthesis of neothramycin was effected from the same intermediate for the synthesis of tomaymycin and SEN-215. During the course of this study, it was found that the quinazoline skeleton was easily formed from o-iodoaniline and five membered lactams. By the application of this method, new synthetic method of quinazoline was developed and vasicinone and rutecarpine were synthesized.